The planar dihydroxo-bridged [Cu-2(dpyam)(2)(mu-OH)(2)I-2].2H(2)O (1) and the roof-shaped trihydroxo-bridged [Cu-2(dpyam)(2)(mu-OH)(3)]Cl. 3H(2)O (2) (in which dpyam = di-2-pyridylamine) dinuclear copper(II) compounds have been synthesized and their crystal structures determined by X-ray crystallographic methods. All of compounds are being centrosymmetric molecule. Compound 1 contains a dinuclear [I(dpyam)Cu(mu-OH)(2)Cu(dpyam)I](+) unit with a strictly planar CuO2 network, dihedral angle between the CuO2 planes of 180degrees. Each copper(II) ion is in a tetrahedrally distorted square pyramidal coordination geometry of the CuN2O2I chromophore with a dihedral angle 19.3degrees between the CuN2 and CuO2 planes. In the dinuclear [(dpyam)Cu(mu-OH)(3)Cu(dpyam)](+) unit of compound 2, the triply bridged Cu(II) ions show a distorted square pyramidal coordination. The fifth apical ligand is a longer bonded bridging OH- group, at distance of 2.433(4) Angstrom, which joins the basal CuN2O2 planes in a roof-shaped configuration with a dihedral angle of 142.5degrees. The Cu-Cu distance is 2.803(7) Angstrom. (C) 2004 Elsevier Ltd. All rights reserved.